Separation of unsaturated hydrocarbons from gas mixtures containing the same



Patented: Jan. 28, an 2,029,120

SEPARATION OF UNSATURATED HYDRO- CARBONS FROM GAS MIXTURES CON- TAINING THE SAME v Heinrich Schilling, Ludwigshaten-on-the-Bhine, and Robert Stadler, Ziegelhausen-on-the-. Neckar, Germany, assignors to I. G. Farbenindustrie Aktiengesellschait, Frankiort-on-the- Main, Germany No Drawing. Application December 3, 1931, Serial No. 578,844. In Germany December 10,

1930 Claims. (Cl. 260-170) The present invention relates to improvements p in the separation of unsaturated hydrocarbons It has already been proposed to remove unsuperatmospherlc pressures. Superatmospheric 5 saturated hydrocarbons, especially acetylene, pressures up to 1000 atmospheres may be em- 5 from gasmixtures containing the same, and to ployed. In case of working with carbon dioxide recover them in an enriched form by treating" it is necessary to work at pressures above 15 atthe gas mixtures, if desired under pressure, at mospheres and at temperatures above 56 below 7 room or lower temperatures with liquids such as zero C.

10 acetone, acetonitrile or water, the dissolved gases The vapors of the solvents which are contained 10 then being expelled from the liquids by heating in the gases leaving the washing plant may be or reducing the pressure. The esters of carbonic readily recovered almost completely, especially acid, the esters and ethers of polyhydric alcowhen washing with the employment of pressure, hols oihigh boiling point and liquid ketones as for example by absorption in water and excontaining more than3carbon atoms in themolepelling again. The unsaturated hydrocarbons 15 cule and boiling above 80 C. have also been may, if desired, be recovered in the form of comproposed as solvents for the said purpose. pounds formed by chemical conversion with the We have now found that the separation of solvent employed, for example by leading the unsaturated hydrocarbons especially of acetylene. unsaturated. hydrocarbons together with a part from gas mixtures containing the same is adof the solvent or the whole solvent in the gaseous 2o vantageouslycarried out by washing the said phase over catalysts. For example by leading gas mixtures with liquefied substances, which mixtures of acetylene and ammonia with an adunder atmospheric pressure are gaseous at 15 C. dition of steam and at a temperature of about and liquid or solid, 1. e. condensable, at a tem- 350 C. over zinc sulphate deposited on silica gel,

perature above 100 below zero C. but diiierent nitrogeneous bases, such as pyridine are obtained. 25 from those chemically converting the unsatu- When carrying out the washing under pressure rated hydrocarbons during the washing treatby the suitable selection of the pressures and/or ment, as for example chlorine, or those which temperatures in the vessels used for washing and are themselves composed oi unsaturated hydroreleasing the pressure. it is i y P le for carbons since in the latter case due to the vapor example to regulate the desired proportions of 30 pressure of the liquid substances it would be im-' acetylene and ammonia for the further workpossible to ensure a purification oi the gases ing up. from unsaturated hydrocarbons and recovering Instead of bringing the vapors oi the solvents the said unsaturated hydrocarbons from the sointo reaction with the unsaturated hydrocarbons lutions thus obtained. Those substances are of which have been washed out, thesevapors which 35 particular advantage which are suitable as coolwhen evolved from the said solvents, for examing agents for refrigerating plants, as for exple by heating or releasing the pressure or both, ample liquid sulphur dioxide, ammonia, carbon contain part of the solvent used, such as amdioxide, methyl chloride and ethyl chloride. The monia, may be led through a liquid absorbing said 40 said liquid substances have an excellent solvent solvent, as for example in the case of ammonia 40 power for unsaturated hydrocarbons, and in parthrough dilute sulphuric acid whereby the amticular for acetylene. The absorptive power of monia is-recovered as ammonium sulphate, while a the said substances for unsaturated hydrocarthe remaining gases leave the washing plant bons is almost as great as that of acetone at the without undergoing any chemical conversion.

same temperatures and at 70 below zero C. ex- Contrasted with the usual solvents with the ex- 46 seeds that, for example of water at 10 C. by ception of water, the solvents employed in acmore than a hundred times. A further advancordance with the present invention, especially tage of the process according to the present insulphur dioxide and ammonia, have the advanvention is that the liquids employed for washing tage 01- being more readily available.

50 out the unsaturated hydrocarbons may also be It has further been found that some of the 60 wholly or partly employed for the attainment of said solvents are eminently suitable for splitting low temperatures, especially for the attainment up mixtures of unsaturated hydrocarbons, in parof the low temperatures required for carrying ticular those of different degrees of saturation, out the washing process itself and this con'stior for the separate recovery of diflerent unsattutes a considerable simplification and (:heapen- 55 from gas mixtures'containing the same.

ing of the operation oi the whole washing plant. The washing treatment according to the present invention may be carried out at ordinary or urated hydrocarbons from gas mixtures containing thesame. With some of the said solvents, the W ratio of the solubilities of acetylene and ethylene is greater than in ithe case of the liquids hitherto used which always absorb considerable amounts of ethylene in addition to the acetylene Thus for example at below aero C. the ratio of the solubilities of acetylene and ethylene in acetone is about 10, whereas in liquid sulphur dioxide 'it is about 15 and in liquid ammonia as much as 100. it a gas mixture containing bothf. acetylene and ethylene is to betreated, the twoi constituentsmay be separated from each other" to a great extent, for example by washing with liquid ainmoniaand may be recovered in a con-f centrated form, the acetylene passing into solu-' tion; this has not been directly possible hitherto. i For example the'gas mixture may be first washed with liquid ammonia in order to dissolve the acetylene almost exclusively. and the ethylene may then be recovered in a second stageby jwashing with sulphur dioxide or one of the usual solvents already mentioned, as for example acetone. Al-fi ternatively, the whole of. the unsaturated hydrocarbons may be first washed out together, as for I example with acetone, the acetylene then being advantageously separated from the expelled gas mixture by means of liquid ammonia. Small amounts of acetylene which still remain in the high percentage ethylene fraction may he'readily hydrogenated into ethylene in the usual manner. A 'further advantage of the employment of the said substances for the separation "of unsaturated hydro carbons consists in the fact that V a very highly concentrated acetylene or ethylene may readily be nbtained. .The iollowing; examples will further illustrate: the natnre or this invention but the invention is not restricted to these examples. i

Example 1 A gas mixture containing per cent of hydro-e "gen, 10 .per cent of acetylene and 5 per; cent of; methane is washed withliquid sulphur dioxide under a pressure or 20 atmospheres at 35 below zero 0., 10 litres oi liquid being allowed to act on each 5 cubic metres or gas mixture measured under normal conditions. The liquid is led from the washing tower into a degasifying vessel heated from below in which it is released from pressure and in which it is heated nearly to the boiling point of the sulphur dioxide. Frequently no special heating means or medium will be re,

- quired, as the heat of thesurrounding air will sot-' flce. When operating under pressure, however heating means may prone necessary. A gas mixture leaves the upper end of the vessel ata temperature of 30 below zero C. which contains per cent oi. acetylene after the absorptionv of the sulphur dioxide contained therein in water. The gas'leaving thezwashing tower still contains 0.4 per cent of acetylene. The liquid sulphur dioxide released from pressure and freed from gas, is

wholly or partly used directly for the production of cold ior the washing plant and passes throughi a jacket surrounding the washing tower, which is constructed as a vaporizer, back into the washe ing tower after heat exchange with the cold L liquid, fl'he sulphur dioxide may also be strongly of 55 below zero C. the contents of the latter acetylene containing ammonia escaping from the washing Example 2 A inixture of '77 per cent 01' hydrogen, 12 per cent of acetylene, 4 per cent of ethylene and? per cent of methane is washed under a pressure of 9 atmospheres at 60 below zero C. first with liquid: ammonia, the ammonia vapor; which is carried along being removed for example by treatment with dilute sulphuric acid.. and then with acetone at the same pressure fand temperature, in a second washer. To each cubic meterjof gas'mixture measured under normal conditions, 0.6 liter of ammonia .is used in the first washer and 4.5 liters of acetone in the second washer. The gas leaving the first washer still contains about 0.5 per cent or acetylene and 4.1 per cent of ethylene and the gas escaping from the second washer contains only 0.2 per cent of acetylene and 0.3 centoi ethylene in .addition to methane and hydrogen. The liquids satnear their boiling point. After heat exchange with the cold liquidsthey pass back into the washing towers. After absorbing the vapors oi solvent from the gasesescaping at a temperature 30 in acetyleneand ethylene amount to 89 per cent and per cent after the first degasifying vessel and 10 per cent and 80 per cent respectively after the second degasifying vessel. :The concentrated 35 first degasifying tower is led at 350 Cfover silica gel laden with zinc sulphate, after the addition or steam, torithe production of pyridine bases. What we claim is: 1. A process for the separation of: acetylene 40 from a gas mixture containing the same which comprises absorbing said acetylene in a liquefied substance which under atmospheric pressure is gaseous at 15 C. and condensable at a tempera ture above below zero C. but different from 4 substances chemically converting said acetylene and from substances composed of an unsaturated hydrocarbon, by washing the'said gas mixture with such liquefied substance.

2. In the process as nlaimed in claim 1, absorb- 50 ing'the acetylene in liquefied sulphur dioxide.

3. In the process as elaimed in claim 1, absorbing the acetylene in liquefied ammonia.

4. A process for the separation 01' acetylene from a gas mxture containing the same which 55 comprises absorbing said acetylene in a liquid which is a cooling agent for refrigerating plants and which is selected from the group consisting of limiefied sulphur dioxide, ammonia, carbon dioxide,

the said gas *mixture with such liquid. 5. processfor the seperation of acetylene and a gagous oleflne from a gas mixture containing the same which comprises washing. said gas mixture with liquefied ammonia at a temperao5 ture above 77? below zero C. and then washing the undissolvegi gas with liquid sulphur. dioxide. HEINRICH scnnmmo. ROBERT ZSTADIER.

methyl chloride and ethyl chloride, by 60 

